Low-foaming detergent compositions

ABSTRACT

THIS INVENTION RELATES TO NON-FOAMING DETERGENT COMPOSITIONS WHICH INCLUDE NONIONIC DETERGENT OR A MIXTURE OF NONIONIC AND ANIONIC DETERGENTS, BUILDER SALT, AND DIALKYL MELAMINE, THE DIALKYLMELAMINE BEING PRESENT IN SUFFICIENT PROPORTION TO MAKE A COMBINATION OF SYNTHETIC DETERGENT(S) AND BUILDER NON-FOAMING OR ESSENTIALLY NON-FOAMING IN WASH WATERS OF USUAL DILUTIONS FOR WASHING MACHINE USE. THE COMPOSITIONS ARE EFFECTIVE LAUNDERING AGENTS, PRIMARILY INTENDED FOR USE IN AUTOMATIC WASHING MACHINES AND IN ALMOST ALL PRACTICAL USES ARE NON-FOAMING, EVEN WHEN USED IN THE NORMALLY FOAM GENERATING HORIZONTAL TUMBER TYPE OF MACHINE.

.jftates 3,826,759 Patented July 30, 1974 3,826,759 LOW-FOAMING DETERGENT COMPOSITIONS Jack T. Inamorato, Westfield, and Robert E. Dickson, ,Belle Mead, N..I., assignors to Colgate-Palmolive Company, New York, N.Y. No Drawing. Filed Feb. 3, 1972, Ser. No. 223,322

' Int. Cl. Clld 3/28, 3/06, 3/08 US. Cl. 252-525 Claims ABSTRACT OF THE DISCLOSURE This invention relates to non-foaming detergent compositions which include nonionic detergent or a mixture of nonionic and anionic detergents, builder salt, and dialkyl melamine, the dialkylmelamine being present in sufficient proportion to make a combination of synthetic detergent(s) and builder non-foaming or essentially non-foaming in wash Waters of usual dilutions for washing machine use. The compositions are effective laundering agents, primarily intended for use in automatic Washing machines and in almost all practical uses are non-foaming, even'when used in the normally foam generating horizontal tumbler type of machine.

BACKGROUND OF THE INVENTION The present invention relates to new synthetic detergent compositions and, more particularly, to compositions based on anionic detergents, nonionic detergents, and mixtures thereof having improved properties. Aqueous solutions of these detergent compositions are characterized by a very low degree of foam formation under conditions of vigorous and continuous agitation.

Although the formation of abundant foam has been considered a desirable property of a washing agent as an indication of lasting detergent power, it is also recognized that copious sudsforrnation is not necessarily a measure of detergent effectiveness. In fact, with certain household and commercial appliances and apparatus, production of copious suds is a handicap rather than an advantage. Compositions of the present invention not only do not foam excessively, but they also have superior detersive properties.

SUMMARY OF THE INVENTION It has now been discovered that the presence of certain dialkylmelamines in detergent compositions consisting essentially of anionic sulfated and sulfonated and nonionic surfactants is effective to achieve a significant enhancement in surface-active properties and a reduction in foaming. More particularly, the improved detergent compositions include water-soluble anionic and nonionic surfac'tants and mixtures thereof, alkaline builder salts, and a minor proportion of a dialkylmelamine effective to suppress the formation of foam in detergent compositions.

The new detergent compositions generate less foam than currently available products, and prevent over-foaming in soft water areas. In addition, the new detergent compositions permit the consumer to use higher levels of detergent before over-foaming occurs.

,Illustrative of the foam-suppressing additives of the present invention are dialkylrnelamines wherein the alkyl group contains from 10 to 18, and preferably from 12 to 1 6, carbon atoms. The most preferred melamine is dilauryl melamine, whichcan be made by reacting cyanuric chloride ,with lauryl amine. I

g. ThQ'IlOVCl compositions of the present invention containas thev active ingredient the anionic sulfated and sulfonated detergents, nonionic detergents, and mixtures thereof. Included therein are the aliphatic sulfated or sulfonated compounds, such as the aliphatic acyl-containing compounds wherein the acyl radical has between 8 and 22 carbon atoms, and, more particularly, the aliphatic carboxylic ester type, containing at least about 10 and preferably between 12 and 26 carbon atoms in the molecule. Among the aliphatic detersive compounds, it is preferred to use the sulfonated aliphatic compounds having between 12 and 22 carbon atoms. As suitable examples of aliphatic detergents may be found, the sulfuric acid esters of polyhydric alcohols incompletely esteri-fied with higher fatty acids, e.g., coconut oil monoglyceride rnonosulfate; the long chain pure or mixed alkyl sulfates, e.g., lauryl sulfate, cetyl sulfate, and higher fatty alcohol sulfates derived from coconut oil hydroxy sulfonated higher fatty acid esters, e.g., higher fatty acid ester of 2,3-dihydroxy propane sulfonic acid; the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic ester of isethionic acid; the higher fatty acid ethanolamide sulfates; the higher fatty acid amides of amino alkyl sulfonic acids, e.g. lauric amide of taurine, and the like.

It is a feature of this invention that the foam-suppressing effects are particularly enhanced when the synthetic detergent comprises primarily a nonionic detergent. The preferred class of nonionic detergents includes the ethoxylation products of hydrophobic hydroxyl compounds such as long chain aliphatic compounds and alkyl aromatic compounds. Among such materials are the polyethyleneoxide condensates of aliphatic alcohols having for example, 8 to 18 carbon atoms, such as lauryl or tallow alcohols, combined with, for example, 3-30 moles of ethylene oxide for each mole of the long chain alcohol.

Other nonionic detergents are the polyethylene oxide condensates of alkyl phenols having, for example, an alkyl group of about 6 to 12 carbon atoms (e.g. nonyl phenol) in which there are a plurality of ethylene oxide units (up to 30) per mole of alkyl phenol. Another class of nonionic detergents includes the polyethylene oxide condensates of higher glycols, which may be made, for exam le, by condensing ethylene oxide with a polypropylene glycol made by reacting propylene oxide and propylene glycol, said polypropylene glycol having a molecular weight of 1500-1800. Again, the nonionic detergent may be made by condensing ethylene oxide with a Water insoluble reaction product (e.g., of molecular weight about 3000) of a diamine (e.g. ethylene diamine) and excess propylene oxide, to incorporate about 4080% of ethylene oxide in the final condensation product. Ethoxylation products of compounds containing mercaptan, rather than hydroxy], groups may also be used.

Other suitable nonionic compounds are the polyoxyalkylene esters of organic acids such as the higher fatty acids, the rosin acids, tall oil acids, acids from petroleum oxidation products, etc. These esters will usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 12 to about 30 moles of ethylene oxide or its equivalent.

Still other useful nonionic surfactants are the alkylene oxide condensates with higher fatty acid amides. The fatty acid group will generally contain from about 8 to about 22 carbon atoms, and this will be condensed withabout 10 to about 50 moles of ethylene oxide as the preferred illustration. The corresponding carbonamides and sulfon-. amides may also be used as substantial equivalents.

In liquid detergents, the active ingredient (surfactant) should preferably be in the form of a highly water. soluble salt, e.g., ammonium, mono, di, and triethanol amine. salts. The liquid detergent composition maybe prepared in dilute or concentrated aqueous solution with or without the presence of a lower molecular weight aliphatic alcohol such as ethyl alcohol, propylene glycol, etc.

The amount of nonionic surfactant that can be present in compositions of the present invention ranges from about 3 2% to about 30%, preferably from about 5% to about by weight based on the final composition.

If the detersive action of an anionic detergent is desired, an anionic detergent may be incorporated in the formulation. The preferred anionic detergents are the alkyl aryl sulfonate detergents, which may be mononuclear or polynuclear in structure. More particularly, the aromatic nucleus may be derived from benzene, toluene, Xylene, phenol, cresols, naphthalene, etc. The alkyl substituent on the aromatic nucleus may vary widely, as long as the desired detergent power of the active ingredient is preserved.

More specific examples of suitable alkyl aromatic sulfonate detergents are the higher alkyl aromatic sulfonate. The higher alkyl substituent may be branched or straightchain in structure; it comprises such groups as octyl, decyl, dodecyl, tridecyl, keryl, pentadecyl, and hexadecyl, mixed long-chain alkyls derived from long-chain fatty materials cracked paraffin wax olefins, polymers of mono olefins, etc. Preferred examples of this class are the higher alkyl mononuclear aryl sulfonates wherein the alkyl group has about 8 to 22, and preferably between 12 and 18 carbon atoms. More particularly, it is preferred to use the higher alkyl benzene sulfonates wherein the higher alkyl group averages between 12 and 16 carbon atoms. For example, propylene may be polymerized to the tetramer and condensed with benzene in the presence of a Friedel-Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulfonation to the desired sulfonate compounds.

These various anionic detergents are generally used in the form of their water-soluble salts, such as the alkali metal, alkaline earth metal, ammonium, amine, and alkylolamine salts. While the sodium potassium, ammonium, and alkylolamine (e.g. mono-, di-, and tri-ethanolamine) salts are preferred ordinarily, other salts such as the lithium, calcium, and magnesium salts may be used if desired. For general use, it is ordinarily preferred to use the sodium and potassium salts. For certain specialized uses, it may be preferred to select the ammonium and alkylolamine salts in view of their generally greater solubility in aqueous solution. The concentration of these watersoluble salts (including suitable mixtures thereof) in the detergent compositions of the present invention is preferably from about 550%. With built compositions, particularly in particulate form, an active ingredient content of 5-50%, and preferably about 10-40% yields highly satisfactory results. Compositions with very high concentrations of these active ingredients are prepared for specialized use generally. Thus in liquid detergent compositions any suitable compositions may be employed, e.g., from about 5% to about 50% of the weight of the total liquid detergent composition.

The presence of conventional amounts of inorganic salt detergent builders, such as various water-soluble inorganic polyphosphates, sulfates, silicates, borates, and carbonates, does not adversely alfect the foaming and detergent properties of the present composition. These builders, the total amount of which may range by weight, based on finished composition, from about 40 to about 90% but more usually between about 45% to about 85%, contribute their different specific effect toward a more satisfactory washing treatment of soiled clothing, dishes, etc.

The most common alkaline builder salts are the phosphates which inhibit the precipitation of alkaline earth materials such as calcium and magnesium compounds in aqueous media. The alkali metal salts, and, more particularly, the sodium and potassium salts, of the chain polyphosphates are usually employed. Examples of such compounds include: sodium tripolyphosphate, potassium acid tripolyphosphate, tetrapotassium pyrophosphate, sodium hexametaphosphate, potassium tetraphosphates and the like. The phosphates are either crystalline substances or glassy, amorphous products. Any water-soluble glassy nvrnnhosohate with mole ratios of alkali oxide to phosphorus oxide of between about 5:3 and about 1:1, and an average chain length of from 3 to several thousands, is suitable for use as a builder in the compositions of the present invention. These phosphates may be the sole builder salts or may be used in combination with any of the aforementioned builder salts.

Where a phosphate free detergent composition is desired the principal builder salts used are the water-soluble alkali metal silicates. Suitable silicates are those having an alkali oxide to silica ratio within a range of about 1:1 to about 1:4, and preferably from about 1:2 to about 1:3. Other builder salts which may be combined with the silicates in phosphate-free compositions include water-soluble alkali metal salts of borates, carbonates, and sulfates.

The soil suspending agents are generally water-soluble or hydrophilic polymeric substances such as the lower alkyl cellulose esters, e.g., methyl cellulose and ethyl cellulose; hydroxyalkyl cellulose esters, e.g., hydroxy cellulose, cellulose ethane sulfonic acid, cellulose glycollic acid; carboxy lower alkyl cellulose compounds, e.g., sodium carboxy methyl cellulose, potassium carboxy methyl cellulose sodium carboxy propyl cellulose, and the like; water-soluble or dispersible synthetic polymeric materials which may be homopolymers, copolymers, graft copolymers, terpolymers, interpolymers, and the like and are illustrated by polyvinyl pyrrolidone, polyvinyl alcohol, by drolyzed polyvinyl acetate, polyacrylic acid, polyacrylamide; maleic anhydride copolymers with alkyl vinyl ethers, e.g., methyl vinyl ether; natural products such as starch and the like.

A small proportion of a higher fatty acid soap may be included in the detergent compositions of the present invention, both for its detersive properties and as a supplemental foam-suppressing agent. The most common water soluble soaps are the alkali metal, ammonium, and alkanolamine soaps derived from mixtures of animal and vegetable fats and oils. The soaps may be considered to be derivatives of higher fatty acids having from 10 to 20, and preferably from 12 to 18, carbon atoms. These fatty acids are obtained from oils, such as coconut oil, palm oil, palm kernel oil, corn oil, cottonseed oil, and olive oil; and animal fats, greases, and oils such as beef tallow, mutton tallow, hog greases, and fish oils. The preferred soaps for the present compositions are alkali metal soaps, for example, the sodium soap of mixed coconut oil and tallow, preferably wherein the mixtures contain a major proportion of tallow and a minor proportion less than 40% of coconut oil. The amount of such anti-foam agent will be from 1.5 to 5 times that of the amine, for best results.

The amount of dialkylmelamine foam suppressing additives is generally minor in proportion to the total detergent composition. Particularly effective results have been achieved when the dialkylmelamine is present in amounts between about /2% and about 15% of the total detergent composition, although it is generally preferred to use from about 1% to about 5% of the additive; The optimum amount of additive and its ratio to the active ingredients will vary according to the specific materials, the contemplated field of application, and manner of use.

Although the essential constituents of the presentcompositions are the synthetic detergent, builder salt, and amine, with soap being a preferred additive to improve antifoam properties, various other materials may also be present, either for their additional efiects or because they are generally carried along with the essential constituents. For example, water, although not required in particulate or solid compositions, is usually present therein to a minor extent. It may be a part of the soap charged or water of hydration with builder salt. In liquid detergent compositions it is the primary solvent and may have with it'lower alkanols, diols, or polyols, such as ethanol, isopropanol, or propylene glycol to improve solubilization of the various ingredients. i

Various filler salts which do not improve detergency but add bulk and sorption capacity for liquid constituents, may be utilized. Thus, sodium sulfate and sodium chloride are good fillers, especially the former. Of the filler salts, those which are hydratable have a capacity for sorption of any excess water which may be present, improving the free flowing nature of the products.

Fluorescent brighteners are frequently used to improve the whitening effect of the detergent on the materials washed. Among these are the various cotton brighteners, polyamide brighteners, polyester brighteners and bleachstable brighteners. These may be the reaction products of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, benzidine sulfone disulfonic acid, aminocoumarins, diphenyl pyrazolene derivatives, or naphthotriazolyl stilbenes. Such materials are described in Stensby, Optical Brighteners and Their Evaluation, a re print of articles published in Soap and Chemical Specialties in April, May, July, August, and September, 1967, especially at pp. 3-5 thereof. The fluorescent dyes or optically active brightener compounds also serve to improve the appearance of particulate detergent compositions containing them, making such compositions appear whiter or brighter.

Various other adjuvants may be present, such as hydrotrope (in the case of liquid compositions), solvents and solubilizing agents (also primarily in liquid compositions), bactericides, fungicides, dyes, water dispersible pigments, chelating agents, antioxidants, stabilizers, and perfumes. Generally, the proportions of such adjuvants will be maintained as low as is feasible, almost always being less than 20% of the composition, frequently less than thereof, and preferably less than 5% thereof. Normally there will be present no more than 5% of any such composition and preferably, in most cases, the amount of adjuvant will be less than 1 or 2%.

To make detergent products in accordance with this invention one needs only to mix the various constituents thereof, with the only critical of difiicult part of the manufacturing method being in addition of the nonionic material and the melamine to the particulate solid material builder or the rest of the detergent product. This can be accomplished by mixing the anti-foam agents with other constituents, less perfume, in an aqueous slurry or crutcher mix and spray drying the slurry (at high pressure, e.g., 200 to 2,000 lbs/sq. inch), into a tower at an elevated temperature, e.g., 150 C. to 300 C., so as to reduce the moisture content thereof to about 10% or less and to produce beads which are generally globular in shape and are in the 6 to 200, preferably 6 to 140 and most preferably, 8 to 100 mesh particle size range (US. Standard Sieve Series). When such a procedure is followed, the crutcher mix, which is heated to about 60 to 90 C. before spraying, will usually contain only limited proportions of the nonionic detergent and melamine because of a tendency of these materials to be flashed away in the spray drying operation and to plume out the top of the spray tower, causing objectionable tower smoking. To avoid such pluming of the high pressure sprayed and atomized droplets it is often desirable to post-add any larger amounts of these materials, and sometimes it is even preferred to spray the crutcher mix without either the nonionic detergent or the melamine and to post-add both of them to the spray dried mixture. Of course, where spray drying is not employed the various granular constituents may be admixed and the liquid ingredients melamine and synthetic detergent, in solid forms may be admixed with the mixture, taking care to distribute them evenly. In such manufacturing methods the particle sizes of the products resulting may be finer and the very fine particles may be removed by screening. Yet, such losses will not be great because the presence of the nonionic detergent and the melamine help to prevent excessive dusting. Thus, such materials will usually also be in the 60 to 200 mesh particle size range. If desired,

all particulate detergents may be screened so as to keep the sizes of particles in the rangesmentioned.

Together with post-additions of liquid ingredients, it is sometimes also'desirable to post-add sodium carboxymethyl cellulose or other gum products which have been found to counter the satisfactory sorption of liquids, such as solutions of melts of the synthetic detergent or higher alkyl amine type, and thereby cause excessive lumping. Thus, in the manufacturing methods, summarized, when small proportions of alkyl melamine and synthetic detergent are used all ingredients may be spray dried together and there will be no objectionable smoking of the spray tower. When powders are used, all ingredients may be mixed together in a blender, such as a Day mixer or ribbon blender and, if desired, may be micropulverized together. When spray dried beads are to be used and proportions of nonionic detergent and amine are greater than 2% of each or greater than a 4% total, the spray drying should be effected with no more than 2% of each such ingredient, preferably no more than 1% of each thereof, in the spray dried product and any additional amounts of these materials should be post-added to the spray dried beads, at which time the synthetic gum or other anti-redeposition agent may also be admixed with the product. If the nonionic detergent and the amine are not liquid they may be melted or dissolved in water or a solvent for spraying onto the detergent builder and other materials. Perfumes and other volatile liquids are usually sprayed onto the particles as a last step, after cooling. If flow of the finished product is not as good as desired there may be added to the detergent composition a flow-inducing agent, such as finely divided particles of Bentonite, clays or other lubricants of which one sold as Satintone is considered to be the best.

The products of this invention are used in the same manner as that in which the commercial synthetic detergents are employed. They may be added to the washing machine before or after clothing, and the machine may be started immediately after addition or starting may be after a substantial time has passed. The water temperature is normally from 15 C. to 75 0., preferably about 60 C. and the concentration of detergent composition is from 0.1 to 0.4%. The product is free flowing and is readily measured out and added to the Washing machine. It foams only slightly in the absence of soil in zero hardness water. When soiled laundry is used, the product does not foam at all. Clothes washed are clean and of excellent whiteness. In comparison with comparable foaming detergents, especially in horizontally tumbling washing machines, reflectometer readings indicate that better washing is obtained with the compositions of this invention.

In the foregoing specification Where the terms minor and major have been employed they signify under 50% and over 50% of the compositions, respectively.

In the foam height tests described below, the following detergent compositions were used:

Chemical Company.

To determine the degree of foam inhibition, foam heights were measured under simulated household-use liters of waterof 150 ppm. hardness at 120 F. containing 0.15% by weight of the test formulation. Three-pounds of terry towels were added. The foam height, in inches, as

viewed through the door window was measured periodically over a ten-minute wash cycle.

"The results of the tests are tabulated in the following table, wherein composition 3 is a commercially available 'loW foaming'detergent composition used for comparison with the compositions of the present invention.

Foam height (inches) Composition 1 2 3 Tim; (minutes):

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrated compositions of the present invention.

Example I A detergent composition is prepared by forming about a 60% solids aqueous slurry containing, on a solids basis, about 10% sodium tridecyl benzene sulfonate, 2% sodium soap of mixed tallow and coco fatty acids, 2% Neodol 4511, 35% sodium tripolyphosphate, 0.5% sodium carboxy methyl cellulose, 0.2% polyvinyl alcohol, 7.0% sodium silicate, 2.0% dilauryl melamine, and 43.3% sodium sulfate. This slurry is spray dried with heated air at a temperature of about 350 F. with a resultant moisture loss of about 40%. The resulting composition is recovered in the form of beads. When tested for foaming and detergency according to the method described supra, the product is found to be non-foaming and of excellent cleaning power, even under the stringent test conditions used. It is found to be far superior to presently available non-foaming or low-foaming detergents under regular use conditions.

Example II Using the procedure of Example I, an improved phosphate-free detergent composition is prepared from the following components:

Percent Neodol 4511 10 Sodium dodecyl benzene sulfonate 5 Sodium silicate 47 Sodium sulfate 35.3 Dicoco melamine 2 Sodium carboxymethyl cellulose 0.5 Optical brighteners, perfume 0.2

The detergent composition produced is essentially nonfoaming under ordinary Conditions, and has excellent cleaning properties.

Example III An improved liquid detergent composition is prepared by blending the following ingredients:

. I 'Percent Neodol 4511 10 Potassium tripolyphosphate" .5 ,Sodium silicate 7.5 Optical brighteners 0.2 Sodium carboxymethyl cellulose 0.3 Dilauryl melamine 1 Sodium sulfate 7 1'5 *Gantrez M-154 1 Water 6O *Polymerized methyl vinyl ether made by General Aniline & Film Corporation.

This liquid detergent composition does not foam in the laboratory tests or under ordinary household use conditions.

The improved detergent formulations of this invention are suitable for use in dilute aqueous solutions in a variety of washing appliances, such as rotary drum or turnbier-type washers, top-loading agitator washers, bottle washers, etc. When so employed, little or no foam is formed with no adverse effect on the detergency characteristics, in operating at temperatures from about 65 to 140 F as commonly used in washing practice. This suppression of suds in accordance with the invention permits employing a larger concentration of the active detergent in the preparation of washing solutions, as compared with the concentrations heretofore considered permissible maxima for tumbler-washer operations. A greater washing efficiency can therefore be achieved. Furthermore, the tendency to froth upon rinsing is substantially obviated.

The low foaming detergent formulations of the present invention can be used in tumbler-type Washers, as well as in any other washing equipment which utilizes conventional high foaming organic detergent materials. In fact, these formulations can be used to reduce foaming in a number of solutions and emulsions which, upon agitation, produce unduly high suds levels, causing spillage and pumping difiiculties, and interfering with a satisfactory filling of containers.

What is claimed is: p

1. A non-foaming detergent composition comprising 2 to 50% of a synthetic organic detergent selected from the group consisting of nonionic and anionic detergents and mixtures thereof 50 to of an inorganic builder salt for the detergent, the combination of detergent and builder giving the composition detergent properties, and 0.5 to 15% of a C to C dialkyl melamine, sufiicient to make the composition non-foaming.

2. A non-foaming detergent composition according to Claim 1 wherein the synthetic organic detergent is a mixture of a nonionic synthetic organic detergent and an anionic synthetic organic sulfonated detergent.

3. A detergent according to Claim 2 wherein the nonionic synthetic organic detergent is a polyethoxylated compound having a lipophilic moiety, the anionic'synthetic detergent is a linear higher alkyl benzene sulfonate, and the builder salt is selected from the group consisting of sodium carbonate, sodium silicate of an Na O:SiO ratio of from 1:1.6 to 1:3, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, pentasodium tripolyphosphate, and pentapotassium tripolyphosphate.

4. A non-foaming detergent composition according to Claim 1 wherein the synthetic organic detergent is a polyethoxylated compound having a lipophilic moiety, and the builder salt is selected from the group consisting of sodium carbonate, sodium silicate of an Na O:SiO ratio of from 1:1.6 to 1:3, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, pentasodium tripolyphosphate and pentapotassium tripolyphosphate.

5. A detergent composition according to Claim 4 which comprises from about 2 to about 30% of a nonionic synthetic organic detergent, which is a polyethoxylated higher alkanol, and from 0.5 to of a di-higher alkyl melamine.

6. A detergent composition according to Claim 5 wherein the polyethoxylated higher alkanol is derived from the condensation of a linear C to C alkanol with from 3 to 30 moles of ethylene oxide, the builder salt is a tetrapotassium pyrophosphate, and the di-higher alkyl melamine is dilauryl melamine.

7. A detergent composition according to Claim 5 which comprises from 5 to 15% of polyethoxylated higher alkanol, the builder salt includes from to 50% of tetrapotassium pyrophosphate, and there is present in the composition from 1 to 5% of an alkali metal higher fatty acid soap.

8. A detergent composition according to Claim 7 wherein the higher fatty acid soap is a sodium soap of a mixture of a major proportion of tallow and a minor proportion, less than 30% of coconut oil, and there is also present from 10 to 70% of sodium silicate, from 5 to 60% of sodium sulfate, and from 0.2 to 5% of sodium carboxymethylcellulose.

9. A detergent composition according to 'Claim 8,

which is in particulate form and comprises a total of 2 to 6% of dicoco melamine and sodium soap, with the proportion of soap being from about 1.5 to 5 times that of the amine to of tetrasodium pyrophosphate, 10 to 35% of sodium silicate, 0.5 to 3% of sodium carboxymethyl cellulose, 5 to 25% of sodium sulfate, and 1 to 10% water.

10. A detergent composition according to Claim 7 wherein the higher alkanol is a mixture of C and C linear primary alcohols condensed with 11 moles of ethylene oxide.

References Cited UNITED STATES PATENTS 3,422,020 I/ 1969 Schmadel et a1 252321 3,679,589 7/ 1972 Schnegelberger 252321 3,285,856 11/1966- Lew 252525 3,325,414 6/1967 Inamorato 252 539 LEON D. ROSDOL, 'Primary Examiner E. L. ROLLINS, Assistant Examiner US. Cl. X.R. 

